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Three‐Dimensional MOF‐Type Architectures with Tetravalent Uranium Hexanuclear Motifs (U 6 O 8 )
Author(s) -
Falaise Clément,
Volkringer Christophe,
Vigier JeanFrançois,
Henry Natacha,
Beaurain Arnaud,
Loiseau Thierry
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201203914
Subject(s) - crystallography , octahedron , uranium , metal organic framework , chemistry , ligand (biochemistry) , metal , x ray photoelectron spectroscopy , zirconium , crystal structure , materials science , inorganic chemistry , adsorption , chemical engineering , organic chemistry , biochemistry , engineering , metallurgy , receptor
Four metal–organic frameworks (MOF) with tetravalent uranium have been solvothermally synthesized by treating UCl 4 with rigid dicarboxylate linkers in N , N ‐dimethylfomamide (DMF). The use of the ditopic ligands 4,4′‐biphenyldicarboxylate ( 1 ), 2,6‐naphthalenedicarboxylate ( 2 ), terephthalate ( 3 ), and fumarate ( 4 ) resulted in the formation of three‐dimensional networks based on the hexanuclear uranium‐centered motif [U 6 O 4 (OH) 4 (H 2 O) 6 ]. This motif corresponds to an octahedral configuration of uranium nodes and is also known for thorium in crystalline solids. The atomic arrangement of this specific building unit with organic linkers is similar to that found in the zirconium‐based porous compounds of the UiO‐66/67 series. The structure of [U 6 O 4 (OH) 4 (H 2 O) 6 (L) 6 ] ⋅ X (L=dicarboxylate ligand; X=DMF) shows the inorganic hexamers connected in a face‐centered cubic manner through the ditopic linkers to build up a three‐dimensional framework that delimits octahedral (from 5.4 Å for 4 up to 14.0 Å for 1 ) and tetrahedral cavities. The four compounds have been characterized by using single‐crystal X‐ray diffraction analysis (or powder diffraction analysis for 4 ). The tetravalent state of uranium has been examined by using XPS and solid‐state UV/Vis analyses. The measurement of the Brunauer–Emmett–Teller surface area indicated very low values (Langmuir <300 m 2 g −1 for 1 , <7 m 2 g −1 for 2 – 4 ) and showed that the structures are quite unstable upon removal of the encapsulated DMF solvent.